N-acylated-amino derivatives of halogenated bicyclo (2, 2, 1) hept-5-en-2-yl compounds



United States Patent Ofiice 3,052,703 Patented Sept. 4, 19,62

The present invention is concerned with organic compounds wherein one terminal position is occupied by a polyhalogenopolycycloalkene and the other terminal position is occupied by an amide or amide derivative. These compounds have been found to possess significant toxicity toward and inhibition of a wide variety of fungi.

The need for efficient and economical fungicidal and fungistatic compositions has long been manifest. In spite of this fact, however, -a number of the compounds employed as fungicides, have generally been found lacking in one or more of the basic requirements of a satisfactory fungicide. In order to be commercially useful a fungicidal composition must be compatible with adjuv-ants and other active ingredients; it must be economical; it should be soluble in common solvents and stable; and most important, it must not be toxic to the plants to which it is applied or to animal life. A prohibitive degree of phyto toxicity under the conditions utilized for fungus control and toxicity toward Warm blooded animals are among the most common shortcomings of present fungicides.

It is consequently the principal object of the present invention to provide new and novel compounds which are effective as fungicides yet do not manifest prohibitive phytotoxicity or toxicity toward warm blooded animals such as man.

Another object of the present invention is to provide new and novel fungicidal compounds which can be economically prepared, distributed and applied to plants.

Yet another object of the present invention is to provide economical and stable fungicidal compositions containing these compounds.

Still another object of the present invention is to provide a method of combating fungi by applying these compositions to plants.

Other objects, features and advantages will be apparent from the following description read in conjunction with the appended claims.

Generally speaking the present invention is concerned with organic compounds wherein one terminal position is occupied by a polyhalogenopolycycloalkene and the other terminal position is occupied by an amide or amide derivative. More specifically, the present invention relates to polyhalogenopolycycloalkenes containing a i N Z group wherein the nitrogen atom lies between the atom attached to the oxygen atom and the polyhalogenopolycycloalkene portion of the molecule. In other words, the nitrogen atom is proximate to the polyhalogenopolycycloalkene portion of the molecule. The second valence bond of the nitrogen atom and the free valence bond of the carbonyl group are occupied by groups defined below. Z, the atom attached to the oxygen atom, is preferably carbon 'but may also be a S or P((O' alky=l)) group. Hence, sulfonamides and phosphoramide are also encompassed by the present invention.

The halogenated cycloalkene portion of the molecule may be attached directly to the nitrogen of the amide portion of the molecule, or alternatively the terminal portions of the molecule may be separated by an alkylene radical of from 1-10 carbon atoms, an arylene radical such as tolylene, phenylene, naphthylene, or an-thrylene group, or an aralkylene group, the alky-lene portion of which contains 1-10 carbon atoms and the aryl portion of which is a tolyl, phenyl, naphthyl or an anthryl group.

Of the polyhalogenopolycycloalkenes which occupy one terminal position of the compounds encompassed by the present invention, halogenated bicyclo(2.2.l)hept-5-ene rings as shown in the following structural formula are preferred Of equal interest is the dimethanonaphthalene ring structure shown in the following structural formula:

The present invention also encompasses the polycyclic structures shown in the following general formula:

In these (formulae X represents hydrogen or halogen (preferably chlorine) and X represents hydrogen, halogen or an alkoxy (preferably met-boxy) group. At least one X should be a halogen.

R may be a straight chain, branched chain or cyclic alkylene group of from 110 carbon atoms both substituted and unsubstituted, ran arylene group such as a tolylene, phenylene, naphthylene or anthrylene or an aralkylene group wherein the alkylene portion contains 1-10 carbon atoms and the aryl portion is chosen from groups such as tolyl, phenyl, naphthalenyl or anthracenyl. Of these R is preferably a straight chain alkyl group of 110 carbon atoms. y is O to 10. When y is 0 the polycyclic ring structure will be connected directly to the nitrogen atom.

Z is carbon, S0 or P(( O alkyl) An example of a compound wherein Z is S0 is N-(l,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept 5-en-2-ylmethyl)benzenesulfonarnide. An example of a compound wherein Z is P ((O alkyl) is diethyl(1,4,5,6,7,7-hexachlorobicyclo (2.2.l)'hept-5-en- 2-ylmethyl)phosphoramidate. Z is preferably carbon.

R may be hydrogen, a straight chain, branched chain or cyclic alkyl group of from 1-10 carbon atoms, both substituted and unsubstituted, an aryl group such as benzyl, tolyl, phenyl, naphthyl or anthryl or an 'aralkyl group, the alkyl portion of which has 1-10 carbon atoms and the aryl portion of which is a benzyl, tolyl, phenyl, naphthyl or anthryl group. In one example one of the substituted alkyl groups which may be employed is the group CH OH CN. R is preferably hydrogen.

R" may be a substituted or unsubstituted aliphatic or olefinic radical, preferably of 1-18 carbon atoms. Straight chain alkyl and olefin radicals are of particular interest. R" may also be a substituted or unsubstituted aryl radical such as a tolyl, phenyl, naphthyl, or anthryl group or substituted or unsubstituted aralkyl group wherein the alkyl portion contains 1-10 carbon atoms and the aryl portion is chosen from groups such as tolyl, phenyl, naphthyl or anthryl group. The groups which may be substituted on t R" include the halogens as in the case of 2-chloro-N- 1,4,5 ,6,7,7 hexachlorobicyclo(2.2.1)hept-S-en-Z-ylmethyl)acetamide and 2-chloro-N-(1,4,5,6,7,7-hexachlorobicyclo 2.2.1 -hept--en-2-ylmethyl) maleamic acid. When R" has substituted thereon a carboxylic group (COOH) the compound may be considered an acid derivative. Of particular interest in this connection are the compounds wherein R is a (CH=CHCOOH) group. Also of interest are compounds wherein R" is a (CH: CHCOOR) R' representing an alkyl radical or metallic ion. In other words, the present invention encompasses, among other acids, certain maleamic acids and the corresponding esters and metallic salts.

Examples of specific compounds encompassed by the present invention follow:

N (1,4,5 ,6,7,7 hexachlorobicyclo (2.2. 1 hept-S-en-Z-ylmethyl] maleamic acid Methyl N-( 1,4,5,6,7,7-hexachlorobicyclo(2.2. 1 )hept-5-en- 2-ylmethyl) maleamate N (1,4,5,6,7,7 hcxachlorobicyclo(2.2.1)hept-S-en-Z-ylmethyl)maleamic acid cupric salt N (1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept-5-en-2-ylmethyl) acetamide 2 chloro-N-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1 )hept-S- en-2-ylmethyl) acetamide N (2 (1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2 yl)ethyl) acetamide N (2 cyanoethyl) N (1,4,5 ,6,7,7-hexachlorobicyclo- (2.2.1 )hept-S -en-2-y1methyl) acetamide N 1,4,5 ,6,7,7-hexachlorobicyclo (2.2.1 )hept-5-en-2-yl) acetamide N ('l,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept-5-en-2-yl)- maleamic acid 2 chloro-N-(1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept-S- en-2-ylmethyl)maleamic acid N (1,4,5,6,7,7 hexachlorobicyclo(2.2.l)hept-5-en-2-ylmethyl) stearamide N 1,4,5 ,6-tetrafluoro-7,7-dimethoxybicyclo 2.2. 1

hept-S-en-Z-yl) decyl) -caproamide N 10-(1,4,5,6,7,7-hexabromobicyclo(2.2.1)hept-5-en-2- yldecyl phenyl) decylbenzlamide N (1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept-S-en-Z-yltolyl)toluamide N (1,4,5 ,6,7,7 hexabromobicyclo(2.2.1)hept-S-en-Z-ylanthryl)naphthamide 2 fluoro N-(1,4,5,6,7,7-hexafluorobicyclo(2.2.1)hept-S- en-2-yln aphthyl) acetamide 2 bromo-N- 1,4,5,6,7,7-hexabromobicyclo(2.2. l hept-S- en-Z-yl) -ethyl) acetamide N methyl N 2-((1,4,5,6,7,7-hexachlorobicyclo(2.2.1)-

hept-S-en-Z-yl) -ethyl) acetamide N 2-decyl) -N-10-( 1,4,5 ,6,7,7-hexachlorobicyclo (2.2. 1

hept-S-en-Z-yl) decyl) acetamide N (decylphenyl) N (5,6,7,8,9,9-hexachloro-1,2,3,4,4a,

5,8,8a octahydro 1,4,5,8-dimethanonaphthalen-Z-yl)- methyl) acetamide N (benzyl) N-I0-(5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,

8a-octahydro-1,4,5,8'dimethanonaphthalen-2-yl)decyl)- acetamide N (tolyl) N 10-(5,6,7,8,9,9-hexabron1o-1,2,3,4,4a,5,8, 8a-octahydro-1,4,5,8-dimethanonaphthalen-2-yl) decyl) acetamide N (2 anthrYD-N-(5,6,7,8,9,9-heXabromo-1,2,3,4,4a,5,8,

8a octahydro l,4,5,8 dimethanonaphthalen 2-yl)- methyl) acetamide N (2 naphthyl)-N-3-(5,6,7,8,9,9-hexabromo-l,2,3,4,4a,

5,8,8a octahyd-ro 1,4,5,S-dimethanonaphthalen-Z-yl)- propyl) acrylamide Generally speaking the amides of the present invention may be made by the addition of corresponding olefinic nitrogen compounds to a hexahalocyclopentadiene. It is also possible in certain cases to hydrogenate the corresponding acetonitrile in acetic anhydride to form the amide. For example, hydrogenation of 1,4,5,6,7,7-hexachlorobicyclo (2.2.1)hept-S-ene-Z-acetonitrile in acetic anhydride yields n-(2- 1,4,5 ,6,7,7-hexachloro-bicyclo(2.2. 1 hept-5-en-2-yl)ethyl)acetamide. The amine salts may be made by reacting the amides with the appropriate acids. Thus, N-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2- yl) acetamide forms the hydrochloride salt of the amine when reacted With HCl. The maleamic acids of the present invention may be made by addition of an inorganic base to the amine salt in alcohol to form the free amine and reacting the free amine so formed with the appropriate acid anhydride. N-(1,4,5,6,7,7-hexach1orobicyclo- (2.2.1)hept-5-en-2-ylmethyl) maleamic acid may thus be made by treating the amine sulfate with NaOH in alcohol and reacting the free amine so formed with maleic anhydride. It will, of course, be readily understood that the salts and esters of these maleamic acids are easily made by reaction with the appropriate base or alchol. A detailed description of the preparation of the amines and amine salts is to be found in copending application, Serial Number 705,781, filed December 30, 1957.

Examples of preparations of compounds encompassed by the present invention follow:

EXAMPLE I N- [1,4,5,6,7,7-Hexachl0r0bicycl0 (2.2.1 )Hept-5-En-2- Ylmethyl M aleamic Acid A solution of 106 g. of 1,4,5,6,7,7-hexachlorobicyclo- (2.2.1)hept-S-ene-Z-methylamiue sulfate made in accordance with Example III of copending application, Serial Number 705,781, filed December 30, 1957, in 100 ml. of methanol was treated with 26 g. of NaOH in 200 ml. of methanol until the solution of the free amine was concentrated under vacuum at 30 and the residue extracted extracted with benzene at 30. The benzene solution of amine was added to 28 g. of maleic anhydride in 100 ml. of benzene with cooling. The maleamic acid which fell out was collected and washed with benzene. The crude melted at 168-171". Recrystallization from acetone gave 25 g. of N-(1,4,5,6,7,7-hexachlorobicyclo(2.2.l)hept-5- 3n-2-ylmethyl)maleamic acid, M.P. 182-184". Workup of the mother liquor gave an additional 59 g. of crude product. Total yield 70% Analysis:

01 Acid eq.

Calcd for CuHgOaN G15 49. 8 428 Found 49. 0, 49. 4 418 EXAMPLE II Methyl N-(],4,5,6,7,7-Hexachlorobicyclo(2.2.1)Hept-S- En-2-Ylmethyl)Maleamate A solution of 42.8 g. of N-(1,4,5,6,7,7-hexachlorob1oyclo(2.2.1)-hept-5-en-2-ylmethyl)maleamic acid in 100 ml. of methanol was refluxed with 5 g. of silica gel catalyst containing sulfuric acid for 16 hours. Filtration of the catalyst and concentration of the filtrate under vacuum gave a sticky semi-solid. Recrystallization from heptane gave 25 g. of methyl n-(1,4,5,6,7,7-hexach1orobicyclo 2.2.1 )hept-S-en-Z-ylrnethyl)maleamate, M.P. ll9121 and 5 g. of solid, M.P. 1 17-120. Total yield 67%.

Analysis:

Cl Calcd for C H NO C1 48.2 Found 48.4

EXAMPLE III N-(I,4,5,6,7,7-Hexachlor0bicycl0(2.2.1 )Hept-S-En- 2-Ylmethyl)Maleamic Acid Cupric Salt 32 g. of N-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-S- en-2-ylmetl1yl)rnaleamic acid was dissolved in dilute NaOH until the solution was alkaline. A solution of 13 g. of cupric sulfate pentahydrate in 400 m1. of water was added and the resulting precipitate Was collected'and water-washed. After drying the blue precipitate, 30 g. of green N-(l,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-S- en-2-ylrnethyl)maleamic acid cupric salt, M.P. 197198 was obtained in 85% yield. Analysis:

Cu CalCd 'fOl' C24H16Cl1 O N2Cll 7.0 Found 7.4

EXAMPLE IV N 1 ,4,5,6,7,7-Hexachlorbicycl0(2 .2 .1 )Hept--En- 2-Ylmethyl) Acetamide Hexachlorocyclopentadiene (81.9 g, 0.3 mole) and N- allylacetamide (29.7 g., 0.3 mole) were mixed together and heated for 40 hours in the presence of a small amount of ditertiarybutyl hydroquinone. The temperature of the reaction mixture was maintained at approximately 125 C. throughout the reaction period. Methanol was added to dissolve the reaction mixture and the solution was treated with charcoal. After removing the charcoal by filtration, 91.7 g. of crude product was obtained from the methanol solution. This represented an 82% yield of N[1,4,5,6,7,7 hexachlorobicyclo(2.2.l)hept 5-en-2-ylmethyl]acetamide based on the theoretical amount possible from the above reactants. Subsequent recrystallization produced a product having a melting point of 170- 171 C. and a chlorine content of 57.1 percent, the theoretical chlorine of the above named acetamide being 57.3 percent.

N- [1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept-5-en-2- ylmethyl1-acetamide, propionamide and butyramide are illustrative of compounds that may be prepared by the addition of the corresponding N-allyl-substituted amides to hexachlorocyclopentadiene.

The corresponding bromo-eompounds may be prepared by using hexabromocyclopentadiene as one of the starting materials. Thus, N-[1,4,5,6,7,7-hexabromobicyclo (2.2.1)hept-S-en-Z-yhnethyl]acetamide may be prepared by reacting hexabromocyclopentadiene and N-allyl-acetamide.

EXAMPLE V Z-Choloro-N- 1 ,4 ,5 ,6,.7,7-H exachlorobicyclo (2 .2 .1 H ep t- 5 -En2 Yl-Methyl Acetamide Cl Calcd for C HgCl NO 61.0 Found 60.6

EXAMPLE VI N-(2-(1,4,5,6,7,7-Hexachlorobicycl0 (2.2.1 )Hept-5-En- 2-Yl) Ethyl)Acetamide 1,4,5,6,7,7 hexachlorobicyclo(2.2.l)hept 5-ene 2 acetonitrile was used as the starting material in the preparation of N-(Z-[l,4,5,6,7,7-hexachlorobicyclo(2.2.1) hept-S-en-Z-yl]ethyD acetamide. 68.0 g. of the above acetonitrile were hydrogenated under pressure for a period of four days in the presence of acetic anhydride (125 ml.) and reduced platinum oxide as catalyst. The initial pressure of the hydrogenation bomb was 61 pounds (gauge) and the external temperature of the vessel was maintained at 35 C. Total pressure drop over this period was 36 pounds. Theoretical pressure drop for the desired reaction being 32 pounds. The volatile materials were then removed from the reaction mixture at reduced pressure (120 C. and 0.5 mm). Analysis or the residue showed a carbon content of 35.1%, hydrogen content of 2.92%, and a chlorine content of 55.2%. Calculated carbon, hydrogen and chlorine content of the above acetamide being 34.2%, 2.85% and 55.2%, respectively. Crystallization of the residue from pentane and ethyl acetate produced a white powdery solid with a melting point of 119-20 0.

EXAMPLE VII N-(1,4,5,6,7,7-Hexachlorobicyclo (2.2.1)Hept-S-En- Z-Yl) Acetamide 1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept 5 en-2-yl methyl ketone oxime was prepared by refluxing a mixture of 300 g. of the ketone, 70 g. of hydroxylamine hydrochloride, 81 g. of anhydrous sodium acetate .110 ml. of water and 450 ml. of methanol on the steam bath for 16 hours. While hot the solution was decanted from the NaCl which had precipitated. The decantate was cooled to 25 and the crude product collected on a filter and washed with water until free of salt. The product had a melting point of 1323 and weighed 313 g. yield). 117 g. of the oxime was slowly added to g. of polyphosphoric acid at 100 C. The mixture was then warmed to The mixture was maintained for 3 hours at 140, allowed to stand overnight at 40, and poured into 2000 ml. of water. The crude product was collected and recrystallized from benzene to give 43 g. of solid, M.P. l6578. Recrystallization from CCL; and

EXAMPLE VIII N (1,4,5,6,7,7 hexaehlorobicyclo(2.2.l)Hept 5 en- 2-yl)-acetamide (140 g.) was dissolved in 500 ml. of hot methanol and 350 ml. of aqueous HCl was added to the solution. The homogeneous solution was refluxed for 4 hours, then cooled, and the precipitated hydrochloride salt of the amine was collected. The crude salt was suspended in 500 m1. of hot water and treated with 20% NaOH solution until the mixture was alkaline to phenolph-thalein. The liberated amine was dissolved in hexane and the hexane extract was concentrated to give 123 g. of crude amine. A solution of 45 g. of maleic anhydride in 300 ml. of benzene was added slowly with cooling to the amine to give the maleamic acid which came out at 'once. After filtration and recrystallization from acetone the product 157 -g., was dried in an oven, M.P. -6

(dec.). Analysis:

Cl Calcdd for C H Cl NO 51.7 Found 51.2

EXAMPLE IX Z-Chloro-N-(1,4,5,6,7,7-Hexachl0r0bicycl0(2.2.1 Hept-5-En-2-Ylmethyl)Maleamic Acid 1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept 5 ene 2- methylamine sulfate (158 g.) made in accordance with Example III of copending application Serial No. 705,781 filed December 30, 1957, was dissolved in 100 m1. of methanol and a solution of 17 g. of NaOH in 500 ml. H O was added to the solution until a penmanent red color to phenolphthalein was obtained. The combined benzene extracts were dried over Na SO and then treated with 5 6 g. of chloromaleic anhydride; an exothermic reaction resulted. The benzene was. boiled oil and the residue was boiled with hexane and filtered hot to give 7 200 g. of product, M.P. 135-45" dec. The product was dissolved in acetone and the acetone was displaced by benzene and cooled to give 48 g. of product M.P.

N (2-C yanoethyl -N -(1 ,4,5 ,6,7,7-H exach lorobicyclo (2.2.1 )Hept-5-En-2Ylmelhyl) Acetamide A solution of 146 g. (0.81 mole) of N-allyl-N-(Z- cyanoethyl)acetarnide and 220 g. (0.81 mole) of hexachlorocyclopentadiene containing 0.1 g. tert-butylhydroquinone was heated at 95 for 7 days. The crude product was dissolved in benzene, the solution was treated hot with charcoal, and filtration and concentration of the filtrate gave crude solid. The solid was collected and recrystallized from benzene-hexane to give 144.5 g. of product, M.P. l2830. Stripping the filtrates of unreacted hexachloro cyclopentadiene in vacuo and recrystallizing the residue from methanol gave an additional 34 g. of product, M.P. 1279 (total yield 49%). Analysis:

Oalcd for CraHrzNaOClu Found EXAMPLE Xl An aqueous solution of 73 g. of 1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-ene 2 rnethylarnine hydrochloride prepared in accordance with the method described in copending application Serial No. 705,7 8 1 filed December 30, 1957, was treated with 20% NaOH and hexane until alkaline. The hexane layer was dried and 14.1 g. of diethyl chlorophosphate added to give an exothermic reaction and a heavy precipitate. Filtration of the solution after the completion of the addition gave 30 g. of the amine hydrochloride. Concentration of the hexane filtrate gave an oil which on cooling solidified to give two crops 7 g. of solid M.P. 94-98, 4.7 g. of solid M.P. 928, and 2.7 g. of solid M.P. 85-98"; total yield 31%.

Recrystallization of the 9498 product gave 5.5 g.

M.P. 96-98 Analysis: P

Calcd 01 C12H15C16NO3 Found 6.10

EXAMPLE XII N-(1,4,5,6,7,7-Hexachlorobicyclo(2.2 .1 )Hept-S-Ene- 2-Ylmethyl)Benzenesulfonamide 9698 Analysis:

Calcd f0! CuHuClaNSOz 45. 3 6. 8 Fnrmrl l 45. 0 6. 7

8 The compounds for the present invention possess fungicidal activity for a wide variety of plant pathogens. In the foliage fungicide screen three varieties of bean plants and tour foil age fungus diseases were employed. Employing these hosts and pathogens the chemicals were screened for general as well as specific control activity and for phytotoxicity.

Diseases and hosts are shown below:

Bean hosts:

Phaseolus vulgaris var. Pinto P. vulgaris var. Black Valentine P. linensis var. Fordhook 242 Uromyces phaseoli var. typica (rust) Erysiphe polygoni (powdery mildew) Colletotrichum lindemuthitmum (anthracnose) Plzytophthora phaseoli (downy mildew) These four bean pathogens are of economic importance and represent each of the four classes of fungi. P. phaseoli is closely allied with P. infestans, the important potato and tomato pathogens. Thus, with the above selection, chemicals can be routinely screened for general or specific disease control activity and for phytotoxioity on a susceptible plant type.

The test is carried out according to the following procedure. Test chemicals are prepared as 1% w./v. stock solutions in a solvent. The stock is diluted for spraying using a diluent consisting of distilled water+solvent ("1:1) or with distilled water-i-two solvents (2:121). Triton X-155, at 0.005% 'W0.1% w. is used as a wetting agent for each concentration of toxicant. All chemicals are initially tested at a single concentration of 1000 ppm. If acceptable disease control is shown, chemicals are retested at 1000 ppm. and the next lowest dilution of 500 ppm. Chemicals continuing to show disease control are retested in this fashion until the effective concentration is determined. Phytotoxicity assessments are expressed as the maximum safe concentration.

Spray applications are made using a laboratory sprayer. The bean plants are selected for use at a stage when the two primary leaves are about three-quarters expanded. To facilitate deposit the primary leaves are oriented to a vertical position by pinning them to a small Wire stall. Either the upper or lower epidermis of the leaf is exposed to the spray stream, depending on the surface to be inoculated.

With the mist type spray and the diluent mixture which is applied, a drying interval of 1-2 hours in suflicient before inoculation with spore suspensions using a specially constructed atomizer. Inoculations with bean mildew are made by dusting conidia over treated plants in the greenhouse. After 24 hours incubation at 19 C. and humidity, the plants are removed to the controlled-environment greenhouse for symptom development. Disease control and phytotoxicity assessments are made within 7 days.

The eflfectiveness of the present compounds as fungicides is further evidenced by the following tests.

To obtain disease control data, chemicals were sprayed as emulsions, solutions or suspensions using concentrations of 0.24% w., 0.12% w, and 0.06% W. These correspond respectively to 2, 1, and 0.5 lbs. toxicant per 100 gallons of spray. Plants were sprayed to the runoff stage, dried for 24 hours, and inoculated with test fungus spores. After inoculation, the plants were held for 24-48 hours in a humidified incubation chamber at 19 C. They were then removed to the greenhouse for disease and phytotoxicity development.

Crops and diseases used were tomato or potato blight (Phytophthora infestans), celery blight (Septoria apiigraveolen tis), bean mildew (Erysiphe p olygoni) bean rust (Uromyces appendiculatus), and cucumber anthracnose (Collototrichum lagenarium').

FOLIAGE FUNGICIDE SCREEN Disease Control, Min. Effective Cone. Phytotoxicity, Max. Safe Conc. (p-p- (op- Chemical Compound Pp. E4). Up. 01. L P. BV

N [1,4,5,6,7,7-Hexachlorobicycl(2.2.1) hept en-lylmethyllmaleamic acid 1, 000 1, 000 1, 000 500 1, 000 l, 000 l, 000 Methyl N (l,4,5,6,7,7 hexachlorobicyclo(2.2.1)

hept-S-en-Z-ylmethyl)maleamatc 250 500 32 16 500 250500 1, 000 N(l,4,5,6,7,7 Hexachl0robicyc1o(2.2.l)hept 5 en-2-ylmethyl)maleamic acid cupric salt 500-1, 000 1, 000 125-250 125-250 1, 000 1, 000 1, 000 2-Chl0r0 -N (1,4,5,6,7,7-hexachlor0bicyclo(2.2.l)

hept-5-en-2-ylmethyl) acetamide 250-500 500 500 1, 000 1, 000 500-1, 000 1, 000 N (2 Cyanoethyl) N (1,4,5,6,7,7 hexachloro bicyclo(2.2.1)hept-5-en-2-ylmethyl)acetamide-.. 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000 N (1,4,5,6,7,7 Hexachlorobicyclo(2.2.l)l1ept 5 en-2-yl)acetamide 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000 N (l,4,5,6,7, Hexachlorobicyclo(2.2.1)hept 5 en-2-yl)maleamic acid 1, 000 1, 000 1, 000 1, 000 1, 000 1,000 1, 000 2- Chloro -N (1,4,5,6,7 ,7-hexacl1lorobicyclo(2.2.1)

hept-5-en-2-ylmethyl)maleamic acid 1, 000 1, 000 500 125 500-1, 000 500-1, 000 500-l, 000

a P4). =Ph1 tophthora phaseoli (downy mildew of lima bean); E.p.=Erysiphe polyqom' (bean powdery mildew); U.p. Uromyces phaseoli (bean rust); C.Z.= Colletotrichum Zindemuthianum (bean anthracnose).

b L=Lima bean; P=Pinto bean; BV=Black Valentine bean.

From four replicated plants per concentration, a percentage disease control figure was obtained, which was based upon the improvement shown over the untreated checks as follows:

(disease rating disease rating) (of untreated check of treatment or standard) disease rating of untreated check The percent disease control for a treatment was next compared with the percent control for the standard fungicide (captan at 0.24% w. of formulated chemical) as follows:

Foliage-Fungicide Activity Index (F-F. A. I.)

Where disease control for the test chemical and standard was equivalent, the index value was (100). Values above 100 indicated superiority.

In most cases comparisons were made at the 0.24% W. (2 lbs/100 gal.) concentration.

Readings for plant injury were obtained on tomatoes, beans, celery and cucumber. Both chronic toxicity (yellowing, distortion, etc.) and acute toxicity (tissue death) were recorded. The scale used was 0-4000 represented no visible poisoning and 400 was the most severe manifestation.

The following table summarized the results of these tests.

Percent control for treatment Percent control for standard X100 tritives, plant hormones and the like. Wetting agents, and if necessary or desirable, stickers such as the heavy hydrocarbon oils with a minimum viscosity of 10 Engler at C. can be present. Any conventional wetting agent, for example, alkyl sulfate salts, alkyl aryl sulfon-ate salts, sulfosuccinate salts, ethers from polyethylene glycols and alkylated phenols, and the like can be employed. If the toxic agents are employed in the form of emulsions or suspensions, for example, in Water, solvents such as oils, emulsifiers, emulsion stabilizers, and the like may be added. Materials which suppress phytotoxic action may also be added if desired. For example, glucose is known to protect tomato plants against damage by certain substances having a phytotoxic effect when employed in concentrated form.

The compounds of the present invention may be applied by means of spraying. Spraying of the plants to be treated may be performed with aqueous emulsions, solutions, or suspensions of the active agents. The spray liquid is generally applied at a rate of from about to 150 gallons per acre. If spraying is eifected with smaller quantities of liquid as in low volume spraying, high concentrations of the active agents should be employed. If desired, a minor amount of the order of about 0.01 to about 0.05% by weight, of a wetting agent may be added to aid in forming a suspension of toxicant in the aqueous medium. Any of the conventional Wetting agents can be 50 employed. Particular suitable wetting agents are the FOLIAGE FUNGICIDE TEST Activity Index at 0.24% Cone. (Upper Phytotoxicity at 0.24% (upper figure) and percent control at 0.06% figure and 0.06% cone. (lower Chemical Compound (lower figure) figure) respectively Com- Com- P.z'. Sta E47. U.a. 0.1. bined '1 C B On bined Index N-(l 4 5 6 7 7-Hexachlorobicyc1o (2.2.1) kept-5- ene-2'ylinethyl)maleamic acid 2 2% IIII: 8 $22 8 175 N (1 4 5 6, 7, 7-Hexachl0robicycl0 (2.2.1) heptfi-en-i-ylmethyl)acetamide *g fa 8 3 8 g? 81 N- (2- (1,4,5,6,7,7-Hexachlor0bicyc1o(2.2.1)hept- 83 100 100 100 100 400 175 acetamde 100 57 70 100 100 35 0 0 100 N-(2-Cyanoethyl)-N-(l,4 5 6, 7 7-hexachlorobi cyclo(2.2.l)hept-5-en-2-yl1ncthyl)acetamide 28 5 8 g g 8 75 11 P.i.=Phytophthora infestans (late blight of tomato); S.a.=Septoria apz'i-graveolentis (late blight of Celery); E.p.=Er1 siphe polygom' (bean powdery mildew); U.a.=Uromyces appendiculatus (bean rust); C.Z.=COZlectotrichum Zagenarz'um (Cucumber Anthracnose) b T=T0mato; C=Celery; B=Bean; Cu=Cucumber.

The active compounds of the present invention may be used alone or in combination with other fungicidal, vericidal, insecticidal or acaricidal materials, the action on which may be either internal or external, with plant nus-odiuin salts of a mixture of secondary heptadecyl sulfates, sold commercially under the trade name of Teepol and polyethylene glycol ethers of alkyl phenols 75 sold under the trade name of Triton X 100 and Triton X-155. Preferably concentrate compositions comprising an active compound of the present invention and a suitable wetting agent are prepared, and the concentrate is then dispersed in water prior to use.

A further form in which the fungicidal compounds of the present invention may be applied consists of solutions of the active ingredient in suitable inert liquid or semi-solid diluents, in which the active ingredient is present in molecularly dispersed form. The form in which the agents to be employed are applied to the objects treated depends on the nature of the object and the purpose of the application.

Suitable inert solvents for the manufacture of liquid preparations should not be readily inflammable, as odorless as possible and without any toxic effect on humans and animals when properly used. Neither should they have a corrosive efiect on the components of the preparations or the material of the storage vessel. Examples of suitable solvents are high boiling oils, e.g., oils of vegetable origin such as castor oil, etc, and lower-boiling solvents with a flash point of at least 30 0., such as carbon tetrachloride, ethylene dichloride, acetylene tetrachloride, hydrogenated naphthalene, sorbent naphtha, etc. Non-aromatic petroleum oils and Xylene are commonly used. Mixtures of solvents may also be used.

The active compounds of the present invention may also be applied in the form of dusts utilizing as the inert vehicle such materials as tricalcium phosphate, precipitated chalk, bentonite, kaolin, and kieselguhr, etc.

These compounds may also be employed in the form of aerosols. For this purpose the active ingredient is dissolved, or dispersed in a solvent boiling below room temperature at atmospheric pressure.

We claim as our invention:

1. A polyhalo compound selected from the group consisting of wherein X is halogen, X is selected from the group consisting of hydrogen, halogen and lower alkoxy, R is selected from the group consisting of alkylene, tolylalkyll 2 carbon atoms, tolyl, phenyl, naphthyl and anthryl, alkenyl of 1 to 18 carbon atoms COOH,

CH CHCOOH and CH=CHCOOR wherein R' is cupric ion.

2. A polychloro compound of the formula wherein R is alkylene of 1 to 10 carbon atoms. 3. A polychloro compound of the formula wherein R is alkylene of 1 to 10 carbon atoms.

4. A polychloro compound of the formula wherein R is alkylene of 1 to 10 carbon atoms and R" is alkyl of 1 to 18 carbon atoms.

5. A polychloro compound of the formula HO III 6. A polychloro compound of the formula wherein R is alkylene of 1 to 10 carbon atoms and R" is alkyl of 1 to 18 carbon atoms.

7. A polychloro compound of the formula wherein R is alkylene of 1 to 10 carbon atoms and R" is alkenyl of 1 to 18 carbon atoms.

8. A polychloro compound of the formula or E 0 wherein R is alkenyl of 1 to 18 carbon atoms. 9. A polychloro compound of the formula 11. Methyl N (1,4,5,'6,7,7 hexachlorobicyclo(2.2.1)- hept-5-en-2-y1methy1)m aleamate.

12. N (1,4,5,6,7,7 hexachlorobieyc1o(2.2.1)hept 5- en-Z-yhnethyDmaleamic a'cid cupric salt.

13. 2 chloro N (1,4,5,6,7,7 hexachlorobicyclo- (2.2.1 )hept-S-en-Z-ylmethyl)acetamide.

14. 2 chloro-N (1,4,5,6,7,7 hexachlorobicyclo- (2.2.1)hept-5en-2-y1methyl)maleamic acid.

References Cited in the file of this patent UNITED STATES PATENTS 14 H Bruce July 25, 1950 Lidov Apr. 21, 1953 Lidov Apr. 21, 1953 Harry May 12, 1953 Dazzi June 16, 1953 Polen et a1. Mar. 23, 1954 Lidov Sept. 13, 1955 Block Nov. 20, 1956 Block Feb. 3, 1959 Wygant Feb. 24, 1959 Boehme et al Nov. 10, 1959 FOREIGN PATENTS Australia Dec. 1, 1955 

1. A POLYHALO COMPOUND SELECTED FROM THE GROUP CONSISTING OF
 12. N - (1,4,5,6,7,7-HEXACHLOROBICYCLO(2.2.1) HEPT - 5EN-2-YLMETHYL)MALEAMIC ACID CUPRIC SALT. 